Two new water-soluble 1,2,3-triazole-containing nona-PEG-branched dendrimers are obtained with nine intradendritic 1,2,3-triazoles (trz). Addition of HAuCl4 in water to these dendrimers quantitatively leads to the intradendritic formation of AuCl3(trz) moieties subsequent to complete Cl- substitution by trz on Au(III), whereas the analogous complexation reaction of AuCl3 with a linear PEG trz ligand forms only an equilibrium between trz-coordinated Au(III) and Au(III) that is not coordinated to trz. Reduction of the dendrimer-Au(III) complexes to Au-0 by NaBH4 then leads to stabilization of gold nanoparticles (AuNPs) in water. The sizes of the AuNPs stabilized by the dendritic macromolecules are further controlled between 1.8 and 12 nm upon selecting the stoichiometry of Au(III) addition per dendritic trz followed by NaBH4 reduction. With a 1:1 Au/trz stoichiometry, the AuNP size depends on the length of the PEG tether of the dendrimer; small dendrimer-encapsulated AuNPs are formed with PEG2000, whereas large AuNPs are formed with PEG550. With Au/trz stoichiometries larger than unity, Au(III) is reduced outside the macromolecule, resulting in the formation of large interdendritically stabilized AuNPs. The formation of very small and only mildly stabilized AuNPs by neutral hydrophilic triazole ligands offers an opportunity for very efficient p-nitrophenol reduction by NaBH4 in water at the AuNP surface.